CN116632397A - Pretreatment system and method for recycling waste lithium ion batteries - Google Patents
Pretreatment system and method for recycling waste lithium ion batteries Download PDFInfo
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- CN116632397A CN116632397A CN202310662666.2A CN202310662666A CN116632397A CN 116632397 A CN116632397 A CN 116632397A CN 202310662666 A CN202310662666 A CN 202310662666A CN 116632397 A CN116632397 A CN 116632397A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 126
- 239000002699 waste material Substances 0.000 title claims abstract description 125
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 77
- 238000004321 preservation Methods 0.000 claims abstract description 19
- 238000002203 pretreatment Methods 0.000 claims abstract description 11
- 239000008247 solid mixture Substances 0.000 claims description 18
- 239000000523 sample Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 7
- 239000002912 waste gas Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000011491 glass wool Substances 0.000 claims description 3
- 239000011490 mineral wool Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 239000011150 reinforced concrete Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000012267 brine Substances 0.000 abstract description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Processing Of Solid Wastes (AREA)
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Abstract
The invention discloses a pretreatment system and a pretreatment method for recycling waste lithium ion batteries, wherein the pretreatment system comprises the following steps: at least one reactor for placing waste lithium ion batteries; the preheating device with an inner cavity is used for preserving heat and preheating a reactor in which the waste lithium ion batteries are placed; the heating crushing device is arranged at intervals with the preheating device and is used for heating the reactor which is subjected to heat preservation and preheating and is provided with the waste lithium ion battery, so that the waste lithium ion battery is crushed and provided with an inner cavity; the conveying device comprises a conveying belt which penetrates through the inner cavities of the preheating device and the heating and crushing device and is used for conveying the reactor with the waste lithium ion batteries to each device. Compared with the traditional recovery process in which complex procedures such as brine discharge, multi-stage crushing and sorting are needed in the pretreatment stage, the pretreatment system provided by the invention can directly crush the waste lithium ion batteries, does not need a brine discharge process, and does not need a gas-shielded pretreatment process.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery recovery, in particular to a pretreatment system and a pretreatment method for waste lithium ion battery recovery.
Background
The lithium ion battery is widely applied to the fields of portable electronic products, power grid energy storage, new energy automobiles and the like due to the advantages of higher energy density, higher voltage, lower memory effect, longer cycle life and the like. With the high-speed development of the global new energy automobile industry, the number of waste lithium ion power batteries is greatly increased. The waste lithium ion battery contains a large amount of heavy metals and organic matters, and if the waste lithium ion battery is discarded at will, the waste lithium ion battery can seriously damage soil and water; meanwhile, the waste lithium ion battery contains a large amount of valuable metal resources, and the grade of the waste lithium ion battery is far higher than the critical exploitation grade of corresponding traditional minerals, so that the waste lithium ion battery has great economic value, and the waste lithium ion battery is recovered, so that the waste lithium ion battery has great significance for environment and economy.
The traditional battery recovery process flow mainly comprises two stages of processes of pretreatment and wet recovery of valuable metals. The pretreatment stage needs to be subjected to the steps of brine discharge, multistage crushing, multistage sorting and the like, wherein the problems of long period, low efficiency, electrolyte leakage, secondary pollution and the like of the brine discharge exist, and the whole crushing process needs gas protection, and has high cost and serious material wrapping. The surface of the crushed and separated anode and cathode mixed waste (black powder) is wrapped with the binder, which seriously affects the wet recovery of valuable metals, so that the binder needs to be removed by high-temperature roasting before the wet recovery leaching process of valuable metals.
Accordingly, the existing recovery technology is still in need of improvement and improvement.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a pretreatment system and a pretreatment method for recycling waste lithium ion batteries, and aims to solve the problems of long pretreatment process period, low efficiency and gas protection requirement of the traditional waste lithium ion batteries.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, a pretreatment system for recycling waste lithium ion batteries is provided, wherein the pretreatment system comprises:
at least one reactor for placing waste lithium ion batteries;
the preheating device is provided with an inner cavity and is used for preserving heat and preheating a reactor in which the waste lithium ion battery is placed;
the heating and crushing device with an inner cavity is arranged at intervals with the preheating device and is used for heating the reactor which is subjected to heat preservation and preheating and is provided with the waste lithium ion battery, so that the waste lithium ion battery is crushed;
the conveying device comprises a conveying belt, the conveying belt penetrates through the inner cavities of the preheating device and the heating and crushing device, and the conveying device is used for conveying the reactor with the waste lithium ion batteries to each device.
Optionally, a first heating element is arranged on the inner wall of the preheating device.
Optionally, a heat preservation material layer is arranged on the outer wall of the preheating device.
Optionally, the thermal insulation material comprises at least one of polyurethane foam, phenolic foam, glass wool, silicon carbide fiber, rock wool, ceramic fiber felt and foaming cement.
Optionally, a second heating element is arranged on the inner wall of the heating and crushing device.
Optionally, a reinforcing plate is arranged on the outer wall of the heating and crushing device.
Optionally, the reinforcing plate is at least one of a steel plate and a reinforced concrete plate.
Optionally, a pipe body is arranged on the outer wall of the reactor, the outer wall of the pipe body is in sealing connection with the outer wall of the reactor, one end of the pipe body penetrates into the reactor, the pipe body is used for detecting the temperature and/or the pressure in the reactor, and a buckle cover is arranged on the pipe body;
or, at least one probe is arranged on the outer wall of the reactor, the probe is in sealing connection with the outer wall of the reactor, one end of the probe penetrates into the reactor, and the probe is used for detecting the temperature and/or the pressure in the reactor.
According to a second aspect of the invention, there is provided a pretreatment method for recycling waste lithium ion batteries based on the pretreatment system for recycling waste lithium ion batteries according to the invention, comprising the steps of:
providing a waste lithium ion battery;
putting the waste lithium ion batteries into a reactor, and then conveying the waste lithium ion batteries into a preheating device through a conveying device to perform heat preservation and preheating;
and conveying the reactor with the waste lithium ion batteries after heat preservation and preheating to a heating and crushing device through a conveying device for heating, so that the waste lithium ion batteries are crushed, and a solid mixture and waste gas are obtained.
Optionally, the temperature of the heat preservation and the preheating is 20-150 ℃.
Optionally, the heating temperature is 150-200 ℃, and the heating time is 15-30 min.
Optionally, the step of obtaining the solid mixture and the exhaust gas further comprises:
and screening the solid mixture, wherein the screened solid mixture is pole powder, and the non-screened solid mixture is a shell and a current collector.
The beneficial effects are that: compared with the traditional pretreatment stage in the recovery process, which requires complex procedures such as discharging salt water, crushing and sorting, the pretreatment system provided by the invention has the advantages that the preheating device is used for carrying out the temperature and preheating on the reactor provided with the waste lithium ion battery, and the heating crushing device is used for heating the reactor provided with the waste lithium ion battery after heat preservation and preheating, so that the waste lithium ion battery is rapidly crushed, the waste lithium ion battery can be directly crushed, the salt water discharging process is not needed, and the gas protection pretreatment process is not needed.
The pretreatment system provided by the invention has the advantages that the reactors are arranged independently, namely, the reactors are arranged separately from the preheating device and the heating and crushing device, and the reactors are transmitted to the devices through the conveying device, so that the production capacity can be enlarged by increasing the number of the reactors. Therefore, the method has the advantages of flexibility, convenience, capability of improving production capacity and the like, and can realize continuous production and improve production efficiency.
According to the invention, the preheating device and the heating crushing device are arranged separately, the preheating device can heat the reactor of the batch, in which the waste lithium ion batteries are placed, and can also heat the reactor of which the unloading is finished after the crushing of the previous batch when the reactor is reused, so that the heat loss of the reactor is avoided (the temperature of the reactor of which the unloading is finished after the crushing of the previous batch is still higher, the preheating device can avoid the loss of part of heat), the energy is saved, the heating time of the reactor of which the waste lithium ion batteries are placed in the heating crushing device can be saved, the daily treatment capacity can be increased, and the pretreatment time can be shortened by the arrangement of the preheating device; the heating and crushing device plays a role in rapidly heating to enable the waste lithium ion batteries to rapidly reach the critical crushing temperature so as to crush the waste lithium ion batteries.
Drawings
Fig. 1 is a schematic diagram of a pretreatment system for recovering waste lithium ion batteries in an embodiment of the invention.
FIG. 2 is a schematic diagram of the structure of a reactor in an embodiment of the present invention.
Detailed Description
The invention provides a pretreatment system and a pretreatment method for recycling waste lithium ion batteries, which are used for making the purposes, the technical scheme and the effects of the invention clearer and more definite, and are further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
According to the invention, when thermal runaway occurs in the waste lithium ion battery, the waste lithium ion battery internal material is subjected to complex chemical reaction to be pulverized, and meanwhile, the internal temperature and pressure of the waste lithium ion battery are continuously increased, and the waste lithium ion battery internal material is flushed out of the battery shell to realize crushing at the moment of reaching the critical crushing temperature.
The embodiment of the invention provides a pretreatment system for recycling waste lithium ion batteries, which is shown in fig. 1 and comprises the following steps:
at least one reactor 1 for placing waste lithium ion batteries;
the preheating device 2 with an inner cavity is used for preserving heat and preheating the reactor 1 in which the waste lithium ion batteries are placed;
the heating and crushing device 3 with an inner cavity is arranged at intervals from the preheating device 2 and is used for heating the reactor 1 which is subjected to heat preservation and preheating and is provided with the waste lithium ion batteries, so that the waste lithium ion batteries are crushed;
the conveying device comprises a conveying belt 4, wherein the conveying belt 4 penetrates through the inner cavities of the preheating device 2 and the heating and crushing device 3, and the conveying device is used for conveying the reactor 1 with the waste lithium ion batteries to each device.
Compared with the traditional pretreatment stage in the recovery process, which requires complex procedures such as brine discharge, multistage crushing and sorting, the pretreatment system provided by the embodiment of the invention has the advantages that the preheating device is used for preserving heat and preheating the reactor in which the waste lithium ion battery is placed, and the heating crushing device is used for heating the preserved and preheated reactor in which the waste lithium ion battery is placed, so that the waste lithium ion battery is rapidly crushed, the waste lithium ion battery can be crushed directly, the brine discharge process is not needed, and the gas protection pretreatment process is not needed.
The reactors in the pretreatment system provided by the embodiment of the invention are arranged independently, namely, the reactors are arranged separately from the preheating device and the heating and crushing device, and the reactors are transmitted to the devices through the conveying device, so that the expansion of the production capacity can be realized by increasing the number of the reactors. Therefore, the method has the advantages of flexibility, convenience, capability of improving production capacity and the like, and can realize continuous production and improve production efficiency.
According to the embodiment of the invention, the preheating device and the heating crushing device are arranged separately, the preheating device can heat the reactor of the batch, in which the waste lithium ion batteries are placed, and can also keep the temperature of the reactor which is discharged after the crushing of the previous batch (or the previous batches) when the reactor is reused, so that the heat loss of the reactor is avoided (the temperature of the reactor which is discharged after the crushing of the previous batch is still higher, the preheating device can avoid the loss of part of heat), the energy is saved, the heating time of the reactor, in which the waste lithium ion batteries are placed, of the heating crushing device is saved, the daily treatment capacity is increased, and the pretreatment time is shortened due to the arrangement of the preheating device; the heating and crushing device plays a role in rapidly heating to enable the waste lithium ion batteries to rapidly reach the critical crushing temperature so as to crush the waste lithium ion batteries.
In this embodiment, the number of reactors in the pretreatment system is at least one, and when the number of reactors is plural, circulation of plural reactors in the pretreatment system can be realized, so that the production efficiency is increased. The invention is not limited to the volume of the reactor, which is illustratively about 60L.
In some embodiments, as shown in fig. 2, a pipe body 11 is disposed on an outer wall of the reactor 1 (the specific number of pipe bodies may be set according to actual needs, the number of pipe bodies in fig. 2 is 3, which is merely illustrative, and the present invention is not limited to the specific number of pipe bodies), the outer wall of the pipe body 11 is connected with the outer wall of the reactor 1 in a sealing manner, and one end of the pipe body 11 extends into the reactor 1, the pipe body 11 is used for detecting the pressure and the temperature in the reactor 1, and a buckle cover (as not shown in fig. 2) is disposed on the pipe body 11, which is not limited to a connection manner of the buckle cover and the pipe body, such as hinging, connectionless separation, and the like. In practice, if the temperature and/or pressure in the reactor are to be known, the buckle cover can be opened, and the temperature and/or pressure test probe can be inserted into the reactor through the pipe body to detect the temperature and/or pressure. In addition, the pipe body can be used for filling and releasing gas. Of course, the invention is not limited to arranging a pipe body on the outer wall of the reactor, detecting the temperature and/or pressure in the reactor can be realized through the pipe body, at least one probe 12 (such as a temperature probe, or a pressure probe, or a temperature and pressure probe) can be directly arranged on the outer wall of the reactor 1, the probe 12 is in sealing connection with the outer wall of the reactor 1, and one end of the probe 12 goes deep into the reactor 1, so that detecting the temperature and/or pressure can be realized.
The preheating device 2 is not limited to a specific volume, the volume of the preheating device can be set according to actual needs, and when the volume of the preheating device is large, more reactors which need to be heated and insulated and are provided with waste lithium ion batteries can be treated at the same time, so that daily treatment capacity is increased, and production efficiency is improved. Specifically, the volume of the inner cavity of the preheating device is 1 times, 1.5 times, 2 times, 2.5 times, 3 times, 4 times, 5 times, etc. that of the inner cavity of the heating and crushing device, and specific times can be set according to actual needs.
In some embodiments, as shown in fig. 1, a first heating element 21 is provided on the inner wall of the preheating device 2. In some embodiments, as shown in fig. 1, a layer of insulating material (not shown in fig. 1) is further provided on the outer wall of the preheating device 2. The heat preservation material layer can effectively ensure that heat is not lost, and simultaneously reduces the energy consumption of the preheating device.
In some embodiments, the first heating element includes, but is not limited to, at least one of a heating wire, a heating plate, and a heating tube.
In some embodiments, the thermal insulation material includes, but is not limited to, at least one of polyurethane foam, phenolic foam, glass wool, silicon carbide fibers, rock wool, ceramic fiber mat, foamed cement.
In some embodiments, as shown in fig. 1, a second heating element 31 is provided on the inner wall of the heating and crushing device 3. In some embodiments, as shown in fig. 1, a reinforcing plate 32 is further provided on the outer wall of the heating and crushing device 3. When the waste lithium ion batteries are heated and crushed, larger pressure can be generated, and therefore, the outer wall of the heating and crushing device is provided with a reinforcing plate.
In some embodiments, a heat insulation lining board (not shown in fig. 1) is further disposed between the inner wall of the heating and crushing device 3 and the second heating element 31.
The invention is not limited to the particular materials of the reinforcement plate, which in some embodiments includes, by way of example, at least one of steel plates, reinforced concrete plates.
In some embodiments, the second heating element includes, but is not limited to, at least one of a heating wire, a heating plate, and a heating tube.
The present invention is not limited to the specific structure of the conveyor (which includes, for example, a head drive mechanism, a conveyor belt, a retracting mechanism, etc.), and is not limited to the specific structure of the conveyor belt, as long as the conveyor belt penetrates through the inner cavities of the preheating device and the heating and crushing device, so long as the conveyance of the reactor in which the waste lithium ion batteries are placed to each device is realized.
As shown in fig. 1, the embodiment of the invention further provides a pretreatment method for recovering waste lithium ion batteries based on the pretreatment system for recovering waste lithium ion batteries, which comprises the following steps:
s1, providing a waste lithium ion battery 5;
s2, placing the waste lithium ion batteries 5 into a reactor 1, and then conveying the waste lithium ion batteries into a preheating device 2 through a conveying device to perform heat preservation and preheating;
and S3, conveying the reactor 1 which is subjected to heat preservation and preheating and contains the waste lithium ion batteries 5 into a heating and crushing device 3 through a conveying device to heat, so that the waste lithium ion batteries are subjected to thermal runaway, the waste lithium ion batteries are triggered to crush, and a solid mixture and waste gas are obtained.
According to the invention, a controllable normal-pressure high-temperature crushing technology (normal pressure refers to normal pressure in the reactor in an initial state, that is, protective gas does not need to be filled into the reactor) is utilized to realize pretreatment of the waste lithium ion battery, so that a solid mixture (a steel shell, a current collector and pole powder) and waste gas are obtained.
In the embodiment of the invention, the waste lithium ion battery comprises an internal battery core, electrolyte and an external battery shell, wherein the battery core comprises a pole piece and a diaphragm, and the pole piece comprises an aluminum foil, a copper foil, and positive and negative electrode materials, a conductive agent and a binder which are loaded on the aluminum foil and the copper foil; the types of the waste lithium ion batteries include, but are not limited to, cylindrical, square shell and soft package.
According to the embodiment of the invention, the reactor containing the waste lithium ion battery is firstly conveyed into the preheating device for heat preservation and preheating, at the moment, the waste lithium ion battery is not broken, after the waste lithium ion battery is conveyed into the heating and breaking device for heating, the internal temperature of the waste lithium ion battery is quickly increased, so that the waste lithium ion battery is in thermal runaway, complex chemical reaction is generated in the waste lithium ion battery during the thermal runaway, internal materials are pulverized to continuously generate gas, a binder and electrolyte react or evaporate in the heating process, a diaphragm and an aluminum foil are melted (the highest temperature in the battery reaches 920 ℃), the internal temperature of the waste lithium ion battery is continuously increased, the pressure is continuously increased, and after the internal temperature of the heating and breaking device reaches 180-200 ℃, the battery is instantaneously broken, and internal materials (active materials and current collectors) are flushed out of a battery shell from a battery sealing position. After crushing, the battery shell (such as a steel shell) and the materials in the battery automatically fall off, so that the battery can be further sorted; the generated waste gas exists in the closed reactor and can be treated by the waste gas recovery device, and the waste gas is discharged after reaching the standard, and the process does not produce secondary pollution.
Compared with the traditional recovery process in which complex procedures such as brine discharge, multistage crushing and sorting are needed in the pretreatment stage, the pretreatment method provided by the embodiment of the invention is based on a simple and flexible pretreatment system, the process is simple and controllable, the controllable crushing of the waste lithium ion battery is realized, the reaction process is rapid, inert gas protection is not needed, the pretreatment time is saved, the production cost is reduced, and the problem that the binder is coated on the surface of the polar powder in the traditional process can be solved.
In the embodiment of the invention, the waste lithium ion batteries to be pretreated can be charged or uncharged, and the charged and uncharged waste lithium ion batteries can be mixed together for pretreatment. When the waste lithium ion battery is electrified, electrification crushing can be realized, and the crushed solid mixture (comprising polar powder, copper foil and aluminum) is sprayed out of the battery shell. When the waste lithium ion battery is not provided with the battery shell, the battery shell can be broken in an electroless way, part of the broken electrode powder is sprayed out of the battery shell, and the copper foil, the aluminum and a small part of the electrode powder are remained in the battery shell. And the charged and uncharged waste lithium ion batteries are mixed together for pretreatment, and the situation after crushing is between the two. In the prior art, the waste lithium ion batteries are pretreated in industry, namely, the waste lithium ion batteries are charged firstly and then crushed, but the waste lithium ion batteries can be directly charged into the reactor for pretreatment in the embodiment of the invention, so that the charged state is not required to be paid attention, and the process is simpler. In addition, the embodiment of the invention has better effect of crushing the charged waste lithium ion battery in the embodiment of the invention, which is contrary to the prior art that the discharge is firstly carried out and then the crushing treatment is carried out.
Taking a cylindrical waste lithium ion battery as an example, after the waste lithium ion battery is broken, black powder (namely active material) and copper foil wash out the tab so that the tab is separated from the steel shell.
In step S3, in some embodiments, the temperature of the preheating and the heat preservation is 20-150 ℃, at this time, the battery is not broken, and some reactions, such as decomposition of the separator, the electrolyte, the binder, etc., occur inside the battery.
In some embodiments, the heating is at a temperature of 150 to 200 ℃ for a time of 15 to 30 minutes. When the heating temperature of the heating and crushing device reaches 150-200 ℃, the inside of the waste lithium ion battery can reach the critical crushing temperature, and at the moment, the internal solid mixture is sprayed out of the battery shell.
In some embodiments, the obtaining the solid mixture and the exhaust gas further comprises the steps of:
and screening the solid mixture, wherein the screened solid mixture is polar powder and is used for subsequent multicomponent separation, and the non-screened solid mixture is a shell and a current collector. The efficient separation of the housing, current collector and active material is achieved.
In summary, compared with the complex procedures of brine discharge, multistage crushing and sorting and the like required in the pretreatment stage of the traditional recovery process, the pretreatment system provided by the invention has the advantages that the preheating device is used for carrying out the temperature and preheating on the reactor in which the waste lithium ion battery is placed, and the heating and crushing device is used for heating the reactor in which the waste lithium ion battery is placed after the heat preservation and the preheating, so that the waste lithium ion battery is crushed rapidly, the waste lithium ion battery can be crushed directly, the brine discharge process is not required, and the gas protection pretreatment process is not required. The pretreatment system provided by the invention has the advantages that the reactors are arranged independently, namely, the reactors are arranged separately from the preheating device and the heating and crushing device, and the reactors are transmitted to the devices through the conveying device, so that the production capacity can be enlarged by increasing the number of the reactors. Therefore, the method has the advantages of flexibility, convenience, capability of improving production capacity and the like, and can realize continuous production and improve production efficiency. According to the invention, the preheating device and the heating crushing device are arranged separately, the preheating device can heat the reactor of the batch, in which the waste lithium ion batteries are placed, and can also heat the reactor of which the unloading is finished after the crushing of the previous batch when the reactor is reused, so that the heat loss of the reactor is avoided (the temperature of the reactor of which the unloading is finished after the crushing of the previous batch is still higher, the preheating device can avoid the loss of part of heat), the energy is saved, the heating time of the reactor of which the waste lithium ion batteries are placed in the heating crushing device can be saved, the daily treatment capacity can be increased, and the pretreatment time can be shortened by the arrangement of the preheating device; the heating and crushing device plays a role in rapidly heating to enable the waste lithium ion batteries to rapidly reach the critical crushing temperature so as to crush the waste lithium ion batteries.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (12)
1. The pretreatment system for recycling the waste lithium ion batteries is characterized by comprising the following components:
at least one reactor for placing waste lithium ion batteries;
the preheating device is provided with an inner cavity and is used for preserving heat and preheating a reactor in which the waste lithium ion battery is placed;
the heating and crushing device with an inner cavity is arranged at intervals with the preheating device and is used for heating the reactor which is subjected to heat preservation and preheating and is provided with the waste lithium ion battery, so that the waste lithium ion battery is crushed;
the conveying device comprises a conveying belt, the conveying belt penetrates through the inner cavities of the preheating device and the heating and crushing device, and the conveying device is used for conveying the reactor with the waste lithium ion batteries to each device.
2. The pretreatment system for recycling waste lithium ion batteries of claim 1, wherein a first heating element is arranged on the inner wall of the preheating device.
3. The pretreatment system for recycling waste lithium ion batteries according to claim 1 or 2, wherein a heat preservation material layer is arranged on the outer wall of the preheating device.
4. The pretreatment system for recycling waste lithium ion batteries according to claim 3, wherein the heat-insulating material comprises at least one of polyurethane foam, phenolic foam, glass wool, silicon carbide fiber, rock wool, ceramic fiber felt and foamed cement.
5. The pretreatment system for recycling waste lithium ion batteries according to claim 1, wherein a second heating member is arranged on the inner wall of the heating and crushing device.
6. The pretreatment system for recycling waste lithium ion batteries according to claim 1 or 5, wherein a reinforcing plate is arranged on the outer wall of the heating and crushing device.
7. The pretreatment system for recycling waste lithium ion batteries of claim 6, wherein the reinforcing plate is at least one of a steel plate and a reinforced concrete plate.
8. The pretreatment system for recycling waste lithium ion batteries according to claim 1, wherein a pipe body is arranged on the outer wall of the reactor, the outer wall of the pipe body is connected with the outer wall of the reactor in a sealing way, one end of the pipe body extends into the reactor, the pipe body is used for detecting the temperature and/or the pressure in the reactor, and a buckle cover is arranged on the pipe body;
or, at least one probe is arranged on the outer wall of the reactor, the probe is in sealing connection with the outer wall of the reactor, one end of the probe penetrates into the reactor, and the probe is used for detecting the temperature and/or the pressure in the reactor.
9. A pretreatment method for recycling waste lithium ion batteries based on the pretreatment system for recycling waste lithium ion batteries according to any one of claims 1 to 8, comprising the steps of:
providing a waste lithium ion battery;
putting the waste lithium ion batteries into a reactor, and then conveying the waste lithium ion batteries into a preheating device through a conveying device to perform heat preservation and preheating;
and conveying the reactor with the waste lithium ion batteries after heat preservation and preheating to a heating and crushing device through a conveying device for heating, so that the waste lithium ion batteries are crushed, and a solid mixture and waste gas are obtained.
10. The pretreatment method according to claim 9, wherein the temperature of the heat preservation and the preheating are each 20 to 150 ℃.
11. The pretreatment method according to claim 9, wherein the heating temperature is 150 to 200 ℃, and the heating time is 15 to 30 minutes.
12. The pretreatment method as recited in claim 9, further comprising the step of, after the obtaining of the solid mixture and the offgas:
and screening the solid mixture, wherein the screened solid mixture is pole powder, and the non-screened solid mixture is a shell and a current collector.
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| CN117531469B (en) * | 2023-10-16 | 2024-06-11 | 南雄市沃太化工有限公司 | Waterproof polyurethane acrylate composite material and preparation device thereof |
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